Gallium nitride doped with rare earth ions and method and structure for achieving visible light emission

ABSTRACT

The present invention is a GaN semiconductor crystal that is doped with at least one RE ion, wherein the structure has been annealed at a temperature of at least about 1,000 degrees Celsius. As a result, the structure is preferably adapted to provide a luminescence spectra over the range from about 380 nanometers to about 1000 nanometers when excited by a suitable excitation. The present invention also includes apparatus and methods for producing cathodoluminesence and electroluminesence that may be suitable for use in any of a wide variety of optoelectronic devices.

This application is a Continuation of U.S. application Ser. No.09/253,170 filed Feb. 20, 1999, now U.S. Pat. No. 6,140,669.

BACKGROUND OF THE INVENTION

The present invention relates generally to rare earth (RE) doped galliumnitride (GaN), and more particularly, to the luminescence of galliumnitride doped with RE ions. In recent years, RE doped semiconductorshave been of considerable interest for possible application in lightemitting devices and for their unique optical and electrical properties.The RE luminescence depends very little on the nature of the host andthe ambient temperature. The GaN and AlN semiconductors doped with Erand co-doped with O have been the most extensively studied. However, thedoping of GaN and AlN with Er and O by molecular beam epitaxy (MBE) andmetal organic chemical vapor deposition (MOCVD) both during epitaxialgrowth and post growth by ion implantation exhibits only infraredemissions at 1.54 μm. In addition, only infrared photoluminescence (PL)spectra have been achieved from GaN implanted with Nd and Er withoutoxygen co-doping.

Recently, two green emission lines at 537 nm and 558 nm were obtainedfrom Er doped GaN grown by solid source MBE on a sapphire substrate. Inaddition, that experiment achieved a broad peak of low intensity blueemission between 480 nm and 510 nm. However, the blue emission haslittle practical utility due to its low intensity. Moreover, theexperiment was unable to achieve luminescence spectra over the rangefrom about 380 nm to about 1000 nm.

In light of the shortcomings of known technology relating to RE dopedGaN, a need exists for an improved RE doped GaN structure that hasincreased industrial applicability. In particular, a need exists for aRE doped GaN structure that is suitable as a material for visibleoptoelectronic devices. A need also exists for a method of manufacturinga RE doped GaN structure that is suitable as a material for visibleoptoelectronic devices.

SUMMARY OF THE INVENTION

The present invention satisfies one or more of the aforementioned needs.A preferred embodiment of the structure of the present inventionincludes a GaN semiconductor crystal that is doped with at least one REion, wherein the structure has been annealed at a temperature of atleast about 1,000 degrees Celsius, and more preferably at about or above1,100 degrees Celsius. As a result, the structure is preferably adaptedto provide a luminescence spectra over the range from about 350-380nanometers to about 900-1000 nanometers when excited by a suitableexcitation.

The GaN may be grown by MBE, MOCVD, or by any other conventionaltechnique. For example, the GaN may be grown on a sapphire substrate.The GaN may be n-type undoped prior to being doped with the RE ion(s).In an alternative embodiment of the present invention, the GaN may bedoped with silicon as well as RE ion(s).

In one embodiment of the structure, the GaN is doped with the RE ion(s)during its growth process. Alternatively, the RE ion(s) may be implantedin the GaN using ion implantation techniques that are well known tothose of ordinary skill in the art. For one example of doping, the GaNsemiconductor crystal is doped with a beam of RE ions that are inclinedat about 10 degrees to the normal of the epilayers of the GaNsemiconductor crystal.

The annealing of the GaN semiconductor crystal is preferably performedunder a flow of N₂ or NH₃. The annealing of the GaN semiconductorcrystal preferably repairs any damage which may have been caused by thedoping of RE ion(s). For example, the annealing preferably repairsdamage to the GaN semiconductor crystal that is caused by theimplantation of the RE ion(s). In addition, the annealing preferablyincorporates the RE ion(s) as an optically active center.

Utilizing a preferred method and structure of the present invention, theApplicant has observed visible cathodoluminescence of the rare earth Dy,Er and Tm implanted in GaN. The implanted samples were given isochronalthermal annealing treatments at a temperature of 1100° C. in N₂ or NH₃,at atmospheric pressure to recover implantation damages and activatedthe rare earth ions. The sharp characteristic emission linescorresponding to Dy³⁺, Er³⁺, and Tm³⁺ intra-4f^(n)-shell transitions,are resolved in the spectral range from 380 nm to 1000 nm, and areobserved over the temperature range of 8.5 K-411 K. Thecathodoluminescence emission is only weakly temperature dependent. Theresults indicate that rare earth-doped GaN epilayers of the presentinvention are suitable as a material for visible optoelectronic devices.

The present invention also includes apparatus and methods for producingcathodoluminesence and electroluminesence that may be suitable for usein any of a wide variety of optoelectronic devices.

In general terms, the method of producing cathodoluminesence comprises:(a) obtaining a gallium nitride crystal, the gallium nitride crystalhaving a dopant of at least one rare earth ion; wherein the structurehas been annealed at a temperature of at least about 1,000 degreesCelsius; and (b) exciting the gallium nitride crystal with an electronbeam so as to cause the crystal to produce cathodoluminesence.

In general terms the method of producing electroluminesence comprises:(a) obtaining a gallium nitride semiconductor crystal, the galliumnitride semiconductor crystal having a dopant of at least one rare earthion; wherein the structure has been annealed at a temperature of atleast about 1,000 degrees Celsius; and (b) placing the gallium nitridesemiconductor crystal in an electric field of sufficient strength so asto cause the gallium nitride semiconductor crystal to produceelectroluminesence.

The present invention also includes devices, such as optoelectronicdevices (e.g., lasers and light-emitting diodes), for producingcathodoluminesence and electroluminesence using the structures andmethods disclosed herein.

The devices and methods of the present invention may be produced usingmanufacturing techniques, mechanical and electronic arrangements andapplication protocols, otherwise known and used in the art.

The Applicants have also observed visible cathodoluminescence of therare earth Sm and Ho implanted in GaN utilized a preferred method andstructure of the present invention. The implanted samples were givenisochronal thermal annealing treatments at a temperature of 1100° C. inN₂ or NH₃, at atmospheric pressure to recover implantation damages andactivated the rare earth ions. The sharp characteristic emission linescorresponding to Sm³⁺ and Ho³⁺ intra-4f^(n)-shell transitions areresolved in the spectral range from 400 nm to 1000 nm, and observed overthe temperature range of 11 K-411 K. The cathodoluminescent emission isonly weakly temperature dependent. The results again indicate that rareearth doped GaN epilayers of the present invention are suitable as amaterial for visible optoelectronic devices.

The Applicant has also observed similar results with Nd doped GaN of thepresent invention. Furthermore, it should be recognized that all otherrare earth ions might be utilized in the present invention. In additionto the novel features and advantages mentioned above, other objects andadvantages of the present invention might become apparent from thefollowing descriptions of the drawings and preferred embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the luminescence spectra of a known Er doped GaNstructure;

FIG. 2 is a graph of the luminescence spectra of a preferred embodimentof a Dy doped GaN structure of the present invention;

FIG. 3 is a graph of the luminescence spectra of a preferred embodimentof an Er doped GaN structure of the present invention;

FIG. 4 is a graph of the luminescence spectra of a preferred embodimentof a Tm doped GaN structure of the present invention;

FIG. 5 is a graph of the luminescence spectra of a preferred embodimentof a Sm doped GaN structure of the present invention;

FIG. 6 is a graph of the luminescence spectra as a function oftemperature of a preferred embodiment of a Sm doped GaN structure of thepresent invention; and

FIG. 7 is a graph of the luminescence spectra of a preferred embodimentof a Ho-doped GaN structure of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT(S)

The present invention is directed to a method and structure forachieving visible light emission comprising GaN doped with RE ion(s).

The Applicants have observed cathodoluminescence (CL) of GaN implantedwith Dy, Er and Tm. Richly structured luminescence spectra attributed toimplanted RE ions are resolved over the wide spectral range from 380 nmto 1000 nm. The cathodoluminescence is strong over the temperature rangefrom 9 K to 411 K.

This is in contrast to the results obtained by Steckl and Birkhahn shownin FIG. 1, which showed only low intensity blue emission and two greenemissions.

The GaN material used for this investigation was grown by MOCVD on thebasal plane of 2-inch diameter sapphire substrates by EMCORE and CREE.The GaN was high quality n-type undoped and silicon doped epilayersimplanted at room temperature with Dy, Er and Tm ions under theconditions shown in Table I which also provided the thicknesses of theGaN layers and electron concentrations. The implanting ion beam wasinclined at 100° to the normal of the GaN epilayers to preventchanneling. The simulated depth profiles, the projected ranges and peakconcentration were calculated using the Pearson distribution (see TableI). The thulium was implanted at three energies at fluences chosen togive an approximation of a square implant profile in the GaN epilayer.This sample was given isochronal thermal annealing treatments (duration30 min) at temperatures from 650 up to 1150° C., in a tube furnace underthe flow of N₂ or NH₃, (purity 99.999) at atmospheric pressure with flowrates of 120 cc/min using the proximity cap method to recoverimplantation damages and incorporate the RE ions as the luminescentcenter. The presence of GaN epilayers after post implantation annealingof the samples was confirmed by measuring x-ray diffraction (XRD)spectra. Samples annealed at temperatures ranging from 650° C. to 900°C. showed no luminescence related to the implanted impurity, while thoseannealed at 1000° C. showed only a weak signal, which indicates thattemperature treatment below 1000° C. is too low to incorporate the REions as the optically active center and recover implantation damages.Only samples annealed above 1000° C. have strong visible CL spectra.

TABLE I Summary of GaN sample and implantation parameters. CalculatedSample Initial electron Thickness Implanted Doses of Projected peakimplanted by concentration of film ion energy implanted ions rangeconcentration ion [10¹⁶ cm⁻³] [μm] [keV] [10⁻¹³ ion/cm²] [nm] [10¹⁹cm⁻³] GaN:Dy 5 1.4 150 100 19.1 3.3 GaN:Si:Dy 50 2.0 150 100 19.1 3.3GaN:Er 5 1.4 150 100 19.8 3.2 GaN:Si:Er 50 2.0 150 100 19.8 3.2 150 10GaN:Tm 0.5 2.25 47 2.8 ˜28 3.9 17 1.5

The cathodoluminescence was excited by an electron beam incident uponthe sample at a 45° angel from an electron gun (Electroscan EG5 VSW)which was in a common vacuum (of ˜5×10⁻⁷ torr ) with the cryostat. Theemitted light was collected by a quartz lens on the entrance slit of thespectrograph-monochromator (ISA model HR-320) operated in Czerny-Turnerconfiguration with different holographic gratings. The optical signalwas detected by a Princeton Instruments back illuminated CCD cameramodel TEA-CCD-512TK with a UV/AR coating and controlled by a computer.

The CL spectra (shown in FIGS. 2, 3 and 4) were recorded at temperature200 K at identical excitation conditions. FIG. 2 shows CL emissionspectra of Dy³⁺ implanted GaN:Si spectrum (1) and GaN spectrum (2). Theassignments for most of the RE³⁺ transitions have been made bycomparisons with data from the literature for the trivalent RE ion(s).These results indicate that the dopant ions were optically active in thetrivalent state. Some of the emission lines can be assigned to severaltransitions and more detailed investigation will clarify our tentativeassignments. The CL spectra exhibit a large number of narrow lines asshown in an insert of FIG. 2 which is an enlargement of spectrum (2) toshow the low intensity lines in the investigated spectral range of 400nm to 950 nm. The characteristic rare earth emission line wavelengthsand assignments are summarized in Table II. FIGS. 3 and 4 show in asimilar manner (with exception of Tm that was only implanted intoundoped GaN), the CL spectra of GaN doped with Er³⁺ and Tm³⁺. As wasmentioned above, we implanted RE³⁺ into undoped GaN and silicon dopedGaN. The emission spectrum (1) in FIG. 3 of GaN:Si:Er is stronger andexhibits more sharp lines than the GaN:Er layer spectrum (2) in FIG. 3.Similar behavior is shown by Dy doped GaN. The different emissionspectra could possibly originate from different types of Dy³⁺ and Er³⁺centers formed in the GaN and GaN:Si. The line at 694 nm that appears inall spectra is the Cr³⁺ emission line originating from the sapphiresubstrate. Apparently, Cr³+ trace impurities in the sapphire substrateare efficiently excited by radiative energy transfer from the rare earthemission of GaN or other excitation mechanisms. We also recordedcathodoluminescence spectra of sapphire substrates after removing GaN:Erepilayers by etching in molten KOH at 200° C. (and on the side of thesapphire substrate without GaN). The absence of a GaN layer on sapphirewas confirmed by XRD analysis, which shows only the presence of Al₂O₃.In both cases, sapphire emission spectra showed only the Cr³⁺ line at694 nm.

TABLE II Summary of RE³⁺ ions line emissions at different temperaturesfrom GaN, GaN:Si (RE)³⁺ λ[nm] λ[nm] λ[nm] Transition ion 11K 200K 411Kassignment Dy 456 ⁴I_(15/2)→⁶H_(15/2) or ⁴G_(11/2→) 481-497 483, 488,503 482, 488 ⁶H_(15/2) 579-594 551, 581, 602 546, 580, 602⁴F_(9/2)→⁶H_(15/2) 671, 684 663, 671 660, 670 ⁴F_(9/2)→⁶H_(13/2) 760-767743, 755, 763 742, 755, 767 (can be Cr³⁺) 845-856 829, 845 827, 843⁴F_(9/2)→⁶H_(9/2) ⁴F_(9/2)→⁶H_(7/2) Er 364 ⁴G_(9/2)→⁴I_(15/2) 383 383⁶G_(11/2)→⁴I_(15/2) 409, 416 414 409 ²H_(9/2)→⁴I_(15/2) 455⁴F_(5/2)→⁴I_(15/2) 479, 488 478, 488 ⁴F_(7/2)→⁴I_(15/2) 515-535 539 539²H_(11/2)→⁴I_(15/2) 560 559, 578 560 ⁴S_(3/2)→⁴I_(15/2) 626 627 625⁴F_(9/2)→⁴I_(15/2) 757, 767 757, 768 ²P_(3/2)→⁴S_(3/2) 818, 829, 839811, 822 ⁴I_(9/2)→⁴I_(15/2) 864-886 866, 873 872 ⁴S_(3/2)→⁴I_(13/2) or⁴I_(9/2)→⁴I_(15/2) 984, 995 989, 1000 987, 1000 ⁴I_(11/2)→⁴I_(15/2) Tm463, 466, 480 463, 466, 479 478 ¹G₄→³H₆ 532, 554, 583, 618 511, 529,544, 585, 618 511, 536, 560, 592 ¹D₂→³H₅ 648, 654 648, 655 ¹G₄→³H₄ or³F₂→³H₆ 776, 790, 804, 812, 844 774, 781, 804, 844 774, 781, 804, 841¹G₄→³H₅

The mechanisms of the nonradiative recombination of the excited statesof a localized RE³⁺ center in semiconductors are the multiphononrelaxation processes, and a migration of energy and cross relaxationprocesses. The probability of the multiphonon relaxation process isdependent upon the type of coupling with the lattice vibrations and thephonon frequency distribution. The results of many studies demonstratethat for ion-host lattice interactions of the RE³⁺ 4f^(n) electrons,weak coupling is characteristic, and the multiphonon emission transitionrates exhibit approximately exponential dependence on the energy gap tothe next lowest level. If the energy gap to the next lower state issufficiently large, the nonradiative multiphonon transition rate isnegligible compared to the radiative rate. This is the situation formost rare earth in nitride semiconductors. The dependency of Dy, Er, andTm doped GaN cathodoluminescence on the temperature depends on ion andthe particular 4f transitions. Generally the temperature quenching isweak, and we observe strong CL emission at 411 K (the detailedexperimental data and analysis will be published elsewhere).

In conclusion, it was demonstrated, for the first time to our knowledge,that rare earth Dy, Er, and Tm ions implanted into GaN afterpost-implantation isochronal annealing at 1100° C. in N₂ or NH₃, atatmospheric pressure can be activated as luminescent centers emitting inthe near UV, visible and infrared regions. The sharp characteristicemission lines corresponding to Dy³⁺, Er³⁺, and Tm³⁺ intra-4f^(n)-shelltransitions are resolved in the spectral range from 380 nm to 1000 nm,and observed over the temperature range of 9 K-411 K. The emissionspectra exhibit a weak temperature dependance that is very important forprospective optoelectronic devices operating at room or highertemperatures. The Ga sites in GaN are the most probable location forrare earth ions in GaN. The outer electron configurations of RE³⁺ ionsare the same 5s²5p⁶. If the RE ions replace Ga in GaN, which areisovalent concerning outer electrons of RE³⁺ ions, they createisoelectronic traps in GaN. The above conclusion is supported by thefact that the atomic covalent radii (ionic RE³⁺) for all rare earthmetals are bigger than atomic radii of Ga that they are replacing, andthe electronegativity of RE elements(1.1-1.25) is smaller than Ga(1.81)for which they substitute. We have evidence that the RE ion in III-Vsemiconductors can occupy different sites (not only substitutional).They can create more complex centers involving other impurities ornative defects.

Rare earth (RE) doped semiconductors have been of considerable interestfor possible application in light emitting devices and for their uniqueoptical and electrical properties. The rare earth luminescence dependsvery little on the nature of the host and the ambient temperature. The4f orbitals of rare earth ions incorporated in semiconductors are sodeeply buried within the electronic shell that the energy levels of the4 f^(n) configuration are only slightly perturbed compared to free ionenergy levels. The electronic structure of the RE luminescence centersand their electrical activities, as well as their indirectphotoluminescence and electroluminescence excitation mechanisms arestill not well understood. The systematic investigation of III-Vsemiconductors doped with rare earth started about two decades ago. Thefirst study of Er doped GaN and AlN was reported by Wilson et al. The1.54 μm photoluminescence (PL), cathodoluminescence (CL) attributed totransitions between Er³⁺ ⁴I_(13/2) and ⁴I_(15/2) was observed in GaN andAlN semiconductors grown by MBE and MOCVD doped both during epitaxialgrowth and post growth by ion implantation. Recently, visible PLemission has been obtained from Er doped GaN grown by MBE on sapphire,and CL emission from GaN grown by MOCVD and implanted by Dy, Er and Tmover the optical range 380-1000 nm.

In this application, we report the first observation of CL of GaNimplanted with Sm and Ho. Richly structured luminescence spectraattributed to trivalent rare earth ions are resolved over the widespectral range from 380 nm to 1000 nm without or with minimal broad bandemission from a GaN host. The cathodoluminescence is strong over thetemperature range from 11 K to 411 K. We have reported similar behaviorrecently for CL emission from Dy, Er, and Tm in GaN.

The GaN material used for this investigation was grown by MOCVD on thebasal plane of 2-inch diameter sapphire substrates by EMCORE and CREE.The GaN was high quality undoped n-type epilayers implanted at roomtemperature with Sm and Ho. The thicknesses of the epilayers, electronconcentrations, and implantation conditions are shown in Table III. Theimplanting ion beam was inclined at 10° to the normal of the GaNepilayers to prevent channeling. The simulated depth profiles, theprojected ranges and peak concentration were calculated using thePearson distribution and are shown in Table III. The samarium andholmium were implanted at three energies at fluences chosen to give anapproximation of a square implant profile in the GaN epilayer. Sampleswere given isochronal thermal annealing treatments (duration 30 min) attemperatures from 650 up to 1150° C., in a tube furnace under the flowof N₂, (purity 99.999) at atmospheric pressure with flow rates of 120cc/min using the proximity cap method to recover implantation damagesand incorporate the rare earth ions as the optically active center. Onlysamples annealed above 1000° C. have strong visible CL spectra. The CLemission spectra presented are obtained from samples annealed at 1100°C., which seems to be the optimal annealing temperature for RE ionsincorporation as the luminescent center.

TABLE III Summary of GaN sample and implantation parameters. ImplantedDoses of Calculated Sample Initial electron Thickness ion implantedProjected peak implanted concentration of film energy ions rangeconcentr. by ion [cm⁻³] [μm] [keV] [ions/cm²] [nm] [cm⁻³] GaN:Sm 5 ×10¹⁶ 1.3 150   1 × 10¹⁴ ˜30 3.3 × 10¹⁹ 45 2.6 × 10¹³ 15 1.3 × 10¹³GaN:Ho 2 × 10¹⁶ 1.8 150   1 × 10¹⁴ ˜28 3.8 × 10¹⁹ 47 2.8 × 10¹³ 17 1.5 ×10¹³

The improved crystal quality of the GaN was visually apparent becausethe samples which had turned brown after the Sm and Ho implantationregained their transparent appearance following annealing. Similarobservation we reported for P, As and Bi implanted into GaN, were therestored crystal quality of GaN after annealing was also confirmed bymeasurement of the Raman spectra.

The samples were mounted on a cold finger cooled by a closed-cyclehelium cryostat operating in temperature ranges from 8.5 K to 411 K. TheCL was excited by an electron beam incident upon the sample at a 45°angel from an electron gun (Electroscan EG5 VSW) which was in a commonvacuum ( of ˜5×10⁻⁷ torr) with the cryostat (the depth of excitation canbe easily varied by varying the electron acceleration voltage between125V and 5 kV). The emitted light was collected by a quartz lens on theentrance slit of the spectrograph-monochromator (ISA model HR-320)operated in Czerny-Turner configurations with different holographicgratings. The optical signal was detected by a Princeton Instrumentsback illuminated CCD camera model TEA-CCD-512TK with a UV/AR coating(spectral range 180 nm-1080 nm) and controlled by a computer.

The CL spectra shown in FIGS. 5, 6 and 7 were recorded at identicalexcitation conditions and different temperatures. Both CL emissionspectra of Sm³⁺ and Ho³⁺ doped GaN at 11 K show a bound exciton toneutral donor peak at 357 nm (3.473 eV), and strong sharp emission linesattributed to the implanted rare earth. FIG. 5 shows CL emission spectraof Sm³⁺ implanted GaN spectrum (1) at 11 K and spectrum (2) at 200 K.The assignments for most of the RE³⁺ transitions have been made bycomparisons with data from the literature for the trivalent rare earthions. These results indicate that the dopant ions were active in thetrivalent state. The characteristic rare earth emission line wavelengthsis summarized in Table IV. Some of the emission lines can be assigned toseveral transitions and more detailed investigation will clarify ourtentative assignments. The CL spectra exhibit a large number of narrowlines as shown in an insert of FIG. 5 which is an enlargement ofspectrum (2) to show the low intensity lines in the investigatedspectral range of 400 nm to 1000 nm.

TABLE IV Summary of RE³⁺ ions line emissions at different temperaturesfrom GaN. (RE)³⁺ λ[nm] λ[nm] λ[nm] Transition ion 11K 300K 411KAssignment Sm 532, 578, 588, 538, 570, 578, 543, 569, 579,⁴G_(5/2)→⁶H_(5/2) 601, 615, 618 605, 615, 619 605, 615 1.⁴G_(5/2)→⁶H_(7/2) 643, 656, 667 656, 668 656, 668 2. 693, 707, 714, 731694, 707, 714, 731 694, 707, 714, 730 ⁴G_(5/2)→⁶H_(9/2) 749, 762 749,762 749, 762 3. 808, 818, 825 791, 810, 818, 830 791, 811, 830, 868 Cr³⁺900, 906, 916, 921, 880, 895, 901, 915, 923, 880, 902, 916, 924⁴G_(5/2)→⁶H_(11/2) 931, 944, 953, 969.7 935, 941, 971 936, 940, 972, 9854. ? ⁴G_(5/2)→⁶F_(5/2) 5. ⁴F_(11/2)→⁶H_(5/2) 6. Ho 501, 526, 548, 555,473, 496, 553, 573, 475, 498, 538, 552, ⁵F₃→⁵I₈ 1. 572, 588 572, 590⁵S₂→⁵I₈ 2. 626 627 627 ⁵F₃→⁵I₇ 3. 664, 671 670 662, 671 Cr³⁺ ? 693, 707,714, 730 693, 707, 714 694, 715 Cr³⁺ 771.6, 775.5, 777, 765, 770, 776,762, 765, 767, 770, ⁵I₄→⁵I₈, 4. 805 805 772, 775, 777, 779 or ⁵S₂→⁵I₇881 870 ⁵I₅→⁵I₈ 5. 964 ˜990 914, 950, 987 ⁵F₅→⁵I₇ 6.

FIG. 6 shows the changes in the CL spectrum of the Sm³⁺ lines withincreasing temperature. Spectra were normalized by taking the 667 nmline of the 100 K spectrum as1. The intensity of this line changesslightly with temperature. FIG. 7 shows the CL spectra of GaN doped withHo³⁺. The emission spectrum (1) in FIG. 7 of GaN: Ho recorded at 11 K,is strong and exhibits two dominant sharp lines at 553 nm and 771.6 nm.The line at 553 nm overlaps on short wavelength side with a broad bandwhich we believed contains unresolved lines with some trace of peaks at501 nm, 526 nm, 548 nm and 572 nm on the longer wavelength side. Theline at 694 nm that appears in all spectra is the Cr³⁺ emission lineoriginating from the sapphire substrate. Apparently, Cr³⁺ traceimpurities in the sapphire substrate are efficiently excited byradiative energy transfer from the rare earth emission of GaN. We alsorecorded cathodoluminescence spectra of the sapphire substrate on theside of the sapphire substrate without GaN. The sapphire emissionspectra showed only the Cr³⁺ line at 694 nm with accompanying weak lineson the shorter (660 nm, 673 nm) and longer (707 nm, 714 nm) wavelengthsides of this line. The emission lines at the shorter wavelength side ofthe 694 nm Cr³⁺ line overlap with very strong Sm³⁺ lines appearing at656 nm and 668 nm. From the spectra in FIG. 5 it is easy to see thatthese lines are the dominant ones in the samarium spectrum over a widerange of temperature.

The positions of the sharp RE ions emission lines shift less than 1 meVover the temperature range 11-400 K. The mechanisms of the nonradiativerecombination of the excited states of a localized RE³⁺ center insemiconductors are the multiphonon relaxation processes, crossrelaxation processes and a migration of energy. Generally thetemperature quenching is weak, and we observe strong CL emission at 411K.

In conclusion, it was demonstrated, for the first time to our knowledge,that rare earth Sm and Ho ions implanted into GaN afterpost-implantation isochronal annealing at 1100° C. in N₂ or NH₃, atatmospheric pressure can be activated as luminescent centers emitting inthe visible and near infrared regions. The sharp characteristic emissionlines corresponding to Sm³⁺ and Ho³⁺ intra-4f^(n)-shell transitions areresolved in the spectral range from 380 nm to 1000 nm, and observed overthe temperature range of 11 K-411 K. The tentative assignment ofobserved emission lines to RE³⁺ 4f^(n) transitions was summarized inTable IV. The emission spectra exhibit a weak temperature dependancethat is very important for prospective optoelectronic devices operatingat room or higher temperatures.

The newly discovered optical activity of RE³⁺ ions in GaN required moredetailed investigations and answers to several questions. One veryimportant question is where the trivalent rare earth ions areincorporated in group III- nitrides AlN, GaN and InN, at substitutionalsites on the metal sublattice and (or) interstitial sites. So far, we donot have experimental data on the electrical activity of RE dopants inIII-nitrides semiconductors. In a hexagonal GaN crystal the Ga atomsoccupy sites of symmetry C_(3v), and two distinct high-symmetryinterstitial positions also have C_(3v) symmetry. The lattice sites ofimplanted radioactive ¹⁶⁷Tm (decay to ¹⁶⁷Er) and ¹⁶⁹Yb(decay to ¹⁶⁹Tm)ions were determined using the emission channeling technique. After roomtemperature implantation, rare earth atoms occupy relaxed Gasubstitutional sites. The transition energies of Sm³⁺ and Ho³⁺ are wellknown from other host crystals and are therefore assigned to transitions(see Figures and Table IV). The levels are due to the spin-orbitcoupling of the 4f^(n) electron configurations. In C_(3v) crystalsymmetry the states with J=5/2, 7/2, 11/2, and 15/2 (Sm³⁺) will split to3, 4, 6, and 8 (doublets), and states with J=0, 1, 2, 3, 4, 5, 6, 7, 8,(Ho³⁺) will split to 1, 1, 1, 3, 3, 3, 5, 5, 5, and 7 (singlet)respectively. Extraction symmetry information of RE centers from thesharp line 4f^(n) optical spectra is difficult, because, contributionsfrom many different centers are superimposed in the range of eachinter-manifold transition. Reliable information can be obtained fromZeeman, polarization and site-selective excitation spectroscopy studies(will be published). Symmetry of center and nature of the lowest Starklevel can be obtained unambiguously from ESR investigation andpoint-charge calculations.

We know from different investigations that Yb substituted for In in InPcreates an isoelectronic trap. The Ga sites in GaN are the most probablelocation for rare earth ions in GaN. The outer electron configurationsof RE³⁺ ions are the same (5s²5p⁶). If the RE ions replace the elementfrom column III in III-nitrides semiconductors that are isovalentconcerning outer electrons of RE³⁺ ions, they create isoelectronic trapsin III-nitrides. The above conclusion is supported by the fact that theatomic covalent radii (ionic RE³⁺) for all rare earth metals are biggerthan atomic radii of Ga and Al that they are replacing. Pauling'selectronegativity of RE elements (1.1-1.25) is smaller than Ga(1.81) andAl(1.61) for which it substitutes. We have evidence that the RE ion inIII-V semiconductors can occupy different sites (not onlysubstitutional). They can create more complex centers involving otherimpurities or native defects. The experimental data of others shows thatRE ions introduce electron or hole traps in III-V semiconductors, and wedo not have any evidence that RE ions act as a donor or acceptor. Therare earth isovalent traps that one might call isoelectronic“structured” impurities possess unfilled 4f^(n) core shells. Itdistinguishes these impurities from the “simple” impurities of maingroup elements of the periodic table. The “simple” impurity typicallyintroduces only effective-mass-like states in the forbidden gap of thehost crystals. The presence of low lying empty core orbitals in rareearth “structured” impurities introduces new excitation andrecombination phenomena. The luminescence structure arises fromintra-configurational 4f—4f transition in the core of the isoelectronic“structured” impurities. The knowledge about the microscopic structureof RE centers in III-nitrides is crucial for understanding theexcitation processes of 4f—4f transitions which in turn can determinethe future of the RE dopants in optoelectronic applications.

Excitation mechanism in cathodoluminescence involves direct impactexcitation of rare earth ions (RE³⁺) by hot electrons, as well as byenergy transfer from electron-hole pairs generated in GaN crystal to the4f^(n) electron system. The direct impact excitation mechanism of RE ³⁺ions in semiconductors, the new step impact electroluminescent device(SIED), and a step photon amplifier converter (SPAC) have beendescribed. The second process most probably involves the RE related“structured” isoelectronic center. The isoelectronic trap can be theelectron or hole trap. Since there is no charge involved, theisoelectronic center forms the bound states by a short rangecentral-cell potential. After an isoelectronic trap has captured anelectron or a hole, the isoelectronic trap is negatively or positivelycharged, and by Coulomb interaction it will capture a carrier of theopposite charge creating a bound exciton. There are three possiblemechanisms of energy transfer. The first is the energy transfer processfrom excitons bound to “structured” isoelectronic centers to the coreelectrons. It takes place as a result of the electrostatic perturbationbetween the core electrons of the “structured” impurity and the exciton,effective-mass-like particles. The second mechanism is the transfer ofenergy to the core electrons, involving the “structured” isoelectronictrap occupied by electron (hole) and free hole (electron) in the valence(conduction) band. The third mechanism is the transfer through aninelastic scattering process in which the energy of a free exciton neara “structured” trap is given to the localized core excited states. Ifthe initial and final states are not resonant, the energy mismatch mustbe distributed in some way, e.g. by phonon emission or absorption. Ifthe atomic core excitations are strongly coupled to the host phonons,the energy transfer probability is likely to be higher. Strong phononcoupling may also be desirable in ensuring that relaxation down theladder of the core excited states occurs quickly, thus preventing backtransfer. However, for efficient radiative recombination, the phononcoupling should not be strong, in order to prevent core de-excitation bynonradiative multiphonon emission. In this regard the rare earth“structured” impurity seems to be ideal.

The preferred embodiments herein disclosed are not intended to beexhaustive or to unnecessarily limit the scope of the invention. Thepreferred embodiments were chosen and described in order to explain theprinciples of the present invention so that others skilled in the artmay practice the invention. Having shown and described preferredembodiments of the present invention, those skilled in the art willrealize that many variations and modifications may be made to affect thedescribed invention. Many of those variations and modifications willprovide the same result and fall within the spirit of the claimedinvention. It is the intention, therefore, to limit the invention onlyas indicated by the scope of the claims.

What is claimed is:
 1. A method of manufacturing a rare earth dopedsemiconductor that is adapted to provide a luminescence spectra over thespectral range from about 350-380 nanometers to about 900-1000nanometers when excited by a suitable excitation, said methodcomprising: growing a gallium nitride semiconductor crystal; doping saidgallium nitride semiconductor crystal with at least one rare earth ion;and annealing said gallium nitride semiconductor crystal at atemperature of at least about 1,000 degrees.
 2. The method of claim 1,wherein said annealing said gallium nitride semiconductor crystal occursat a temperature of at least about 1,100 degrees.
 3. The method of claim1 wherein the gallium nitride is grown by MBE or MOCVD.
 4. The method ofclaim 3 wherein the gallium nitride is doped with said at least one rareearth ion during its growth process.
 5. The method of claim 3 whereinsaid at least one rare earth ion is implanted in the gallium nitride. 6.The method of claim 5 wherein damage to said gallium nitridesemiconductor crystal caused by the implantation of said at least onerare earth ion is substantially repaired by the annealing.
 7. The methodof claim 1 wherein the annealing is performed under a flow of N₂ or NH₃.8. The method of claim 1 wherein said gallium nitride semiconductorcrystal is doped with a beam of rare earth ions that are inclined atabout 10 degrees to the normal of the epilayers of said gallium nitridesemiconductor crystal.
 9. The method of claim 1 wherein the galliumnitride is n-type undoped.
 10. The method of claim 1 wherein saidgallium nitride semiconductor crystal is also silicon-doped.
 11. Themethod of claim 1 wherein said at least one rare earth ion is Nd³⁺,Sm³⁺, Dy³⁺, Ho³⁺, Er³⁺, or Tm³⁺.
 12. The method of claim 1 wherein saidgallium nitride semiconductor crystal is grown on a sapphire substrate.13. A method of producing cathodoluminesence comprising: (a) obtaining agallium nitride crystal, said gallium nitride crystal having a dopant ofat least one rare earth ion; wherein said structure has been annealed ata temperature of at least about 1,000 degrees Celsius; and (b) excitingsaid gallium nitride crystal with an electron beam so as to cause saidcrystal to produce cathodoluminesence.
 14. A method of producingelectroluminesence comprising: (a) obtaining a gallium nitridesemiconductor crystal, said gallium nitride semiconductor crystal havinga dopant of at least one rare earth ion; wherein said structure has beenannealed at a temperature of at least about 1,000 degrees Celsius; and(b) placing said gallium nitride semiconductor crystal in an electricfield of sufficient strength so as to cause said gallium nitridesemiconductor crystal to produce electroluminesence.